Hydrogen transfer and isoparaffin-olefin alkylation process

ABSTRACT

The transfer of hydrogen from a paraffin to an olefin is provided. This reaction may be carried out in the presence of a catalyst, such as MCM-36. Especially when the paraffin reactant is an isoparaffin, the olefin produced from the reacted isoparaffin may react with unreacted isoparaffin to also produce an alkylate product.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.07/929,547, filed Aug. 13, 1992, now U.S. Pat. No. 5,326,922.

BACKGROUND

The present invention relates to an isoparaffin-olefin alkylation andhydrogen transfer process to provide a product useful, inter alia, as anoctane enhancer for gasoline.

As a result of the curtailment in the use of tetraethyl lead as anoctane-improving additive for gasoline, not only has the production ofunleaded gasoline increased but the octane number specification of allgrades of gasoline have increased as well. Isoparaffin-olefin alkylationis a key route to the production of highly branched paraffin octaneenhancers which are to be blended into gasolines.

Alkylation involves the addition of an alkyl group to an organicmolecule. Thus, an isoparaffin can be reacted with an olefin to providean isoparaffin of higher molecular weight. Industrially, alkylationoften involves the reaction of C₂ -C₅ olefins with isobutane in thepresence of an acidic catalyst. Alkylates are valuable blendingcomponents for the manufacture of premium gasolines due to their highoctane ratings.

In the past, alkylation processes have included the use of hydrofluoricacid or sulfuric acid as catalysts under controlled temperatureconditions. Low temperatures are utilized in the sulfuric acid processto minimize the undesirable side reaction of olefin polymerization andthe acid strength is generally maintained at 88-94 percent by thecontinuous addition of fresh acid and the continuous withdrawal of spentacid. The hydrofluoric acid process is less temperature-sensitive andthe acid is easily recovered and purified.

The typical types of alkylation currently used to produce high octanegasoline blending component, that is, the hydrofluoric acid and sulfuricacid alkylation processes, have inherent drawbacks includingenvironmental concerns, acid consumption and disposal of corrosivematerials. With the increasing demands for octane and the increasingenvironmental concerns, it has been desirable to develop an alkylationprocess based on a solid catalyst system. A solid catalyst offers arefiner a more environmentally acceptable alkylation process than thecurrently used hydrofluoric and sulfuric acid alkylation processes.

Crystalline metallosilicates, or zeolites, have been widely investigatedfor use in the catalysis of isoparaffin-olefin alkylation. For example,U.S. Pat. No. 3,251,902 describes the use of a fixed bed ofion-exchanged crystalline aluminosilicate having a reduced number ofavailable acid sites for the liquid phase alkylation of C₄ -C₂₀branched-chain paraffins with C₂ -C₁₂ olefins. The patent furtherdiscloses that the C₄ -C₂₀ branched-chain paraffin should be allowed tosubstantially saturate the crystalline aluminosilicate before the olefinis introduced to the alkylation reactor.

U.S. Pat. No. 3,450,644 discloses a method for regenerating a zeolitecatalyst used in hydrocarbon conversion processes involving carboniumion intermediates.

U.S. Pat. No. 3,549,557 describes the alkylation of isobutane with C₂-C₃ olefins using certain crystalline aluminosilicate zeolite catalystsin a fixed, moving or fluidized bed system, the olefin being preferablyinjected at various points in the reactor.

U.S. Pat. No. 3,644,565 discloses the alkylation of a paraffin with anolefin in the presence of a catalyst comprising a Group VIII noble metalpresent on a crystalline aluminosilicate zeolite, the catalyst havingbeen pretreated with hydrogen to promote selectivity.

U.S. Pat. No. 3,647,916 describes an isoparaffin-olefin alkylationprocess featuring the use of an ion-exchanged crystallinealuminosilicate, isoparaffin/olefin mole ratios below 3:1 andregeneration of the catalyst.

U.S. Pat. No. 3,655,813 discloses a process for alkylating C₄ -C₅isoparaffins with C₃ -C₉ olefins using a crystalline aluminosilicatezeolite catalyst wherein a halide adjuvant is employed in the alkylationreactor. The isoparaffin and olefin are introduced into the alkylationreactor at specified concentrations and catalyst is continuouslyregenerated outside the alkylation reactor.

U.S. Pat. No. 3,893,942 describes an isoparaffin-olefin alkylationprocess employing, as catalyst, a Group VIII metal-containing zeolitewhich is periodically hydrogenated with hydrogen in the gas phase toreactivate the catalyst when it has become partially deactivated.

U.S. Pat. No. 3,236,671 discloses the use, in alkylation, of crystallinealuminosilicate zeolites having silica to alumina mole ratios above 3and also discloses the use of various metals exchanged and/orimpregnated on such zeolites.

U.S. Pat. No. 3,706,814 discloses another zeolite catalyzedisoparaffin-olefin alkylation process and further provides for theaddition of C₅ + paraffins such as Udex raffinate or C₅ + olefins to thealkylation reactor feed and the use of specific reactant proportions,halide adjuvants, etc. U.S. Pat. No. 3,624,173 discloses the use, inisoparaffin-olefin alkylation, of zeolite catalysts containinggadolinium.

U.S. Pat. No. 3,738,977 discloses alkylation of paraffins with ethyleneemploying a zeolite catalyst which possesses a Group VIII metalcomponent, the catalyst having been pretreated with hydrogen.

U.S. Pat. No. 3,865,894 describes the alkylation of C₄ -C₆ isoparaffinwith C₃ -C₉ monoolefin employing a substantially anhydrous acidiczeolite, for example acidic zeolite Y (zeolite HY), and a halideadjuvant.

U.S. Pat. No. 3,917,738 describes a process for alkylating anisoparaffin with an olefin using a solid, particulate catalyst capableof absorbing the olefin. The isoparaffin and the olefin are admixed toform a reactant stream in contact with catalyst particles at theupstream end of an adsorption zone after which the reactants are passedconcurrently with the catalyst so that a controlled amount of olefin isadsorbed onto the catalyst before the combination of reactants andcatalyst is introduced into an alkylation zone. This controlled olefinadsorption is said to prevent polymerization of the olefin duringalkylation.

U.S. Pat. No. 4,377,721 describes an isoparaffin-olefin alkylationprocess utilizing, as catalyst, ZSM-20, preferably HZSM-20 or rare earthcation-exchanged ZSM-20.

U.S. Pat. No. 4,384,161 describes a process of alkylating isoparaffinswith olefins to provide alkylate employing as catalyst a large porezeolite capable of absorbing 2,2,4-trimethylpentane, e.g., ZSM-4,ZSM-20, ZSM-3, ZSM-18, zeolite Beta, faujasite, mordenite, zeolite Y andthe rare earth metal-containing forms thereof, and a Lewis acid such asboron trifluoride, antimony pentafluoride or aluminum trichloride. Theuse of a large pore zeolite in combination with a Lewis acid inaccordance with this patent is reported to greatly increase the activityand selectivity of the zeolite thereby effecting alkylation with higholefin space velocity and low isoparaffin/olefin ratio.

U.S. Pat. Nos. 4,992,615; 5,012,033; and 5,073,665 describe anisoparaffin-olefin alkylation process utilizing, as a catalyst, azeolite designated as MCM-22.

SUMMARY

There is provided a dual process for converting an isoparaffin feed anda branched C₅ + olefin feed, said process comprising contacting bothsaid isoparaffin feed and said olefin feed under conditions sufficientto cause the following two results:

(a) the transfer of hydrogen from said isoparaffin feed to said olefinfeed, whereby isoparaffin feed is converted into olefin product andolefin feed is converted into a first branched paraffin product, saidolefin product being different from said olefin feed; and

(b) said olefin product from step (a) self alkylates with unreactedisoparaffin in said isoparaffin feed to produce a second branchedparaffin product having the number of carbon atoms equal to the sum ofthe carbon atoms in the olefin and isoparaffin which are reactedtogether in this step (b).

Since the isoparaffin reactant in the second reaction reacts with anolefin which is produced from the same isoparaffin in the firstreaction, this alkylation reaction is referred to herein as aself-alkylation reaction.

There is also provided a process for preparing branched paraffins, saidprocess comprising the steps of:

(a) cracking hydrocarbons to produce a product comprising branchedolefins having at least 5 carbon atoms;

(b) contacting the C₅ + branched olefins of step (a) with an isoparaffinfeed under hydrogen transfer conditions, whereby isoparaffin feed isconverted into an olefin product and said C₅ + branched olefins areconverted into a first branched paraffin product; and

(c) contacting said olefin product from step (b) with unreactedisoparaffin in said isoparaffin feed under alkylation conditions toproduce a second branched olefin product having the number of carbonatoms equal to the sum of the carbon atoms in the olefin and isoparaffinwhich are reacted together in step (c), wherein steps (b) and (c) takeplace simultaneously in the same reactor.

There is also provided a process for preparing branched paraffins, saidprocess comprising the steps of:

(a) oligomerizing olefins to produce a product comprising branchedolefins having at least 5 carbon atoms;

(b) contacting the C₅ + branched olefins of step (a) with an isoparaffinfeed under hydrogen transfer conditions, whereby isoparaffin feed isconverted into an olefin product and said C₅ + branched olefins areconverted into a first branched paraffin product; and

(c) contacting said olefin product from step (b) with unreactedisoparaffin in said isoparaffin feed under alkylation conditions toproduce a second branched olefin product having the number of carbonatoms equal to the sum of the carbon atoms in the olefin and isoparaffinwhich are reacted together in step (c), wherein steps (b) and (c) takeplace simultaneously in the same reactor.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray diffraction pattern of an as-synthesized form of alayered material which may be swollen and pillared.

FIG. 2 is an X-ray diffraction pattern of a swollen form of the materialhaving the X-ray diffraction pattern shown in FIG. 1.

FIG. 3 is an X-ray diffraction pattern of the pillared form of thelayered material having the X-ray diffraction pattern shown in FIG. 1.

FIG. 4 is an X-ray diffraction pattern of the calcined form of theswollen material having the X-ray diffraction pattern shown in FIG. 2.

EMBODIMENTS

Isoparaffin-light olefin alkylation plays an important role in themanufacture of high octane gasoline blending stocks with alkylatetypically comprising 10-15% of the gasoline pool. Alkylate is anespecially valuable component of the gasoline pool as it possesses bothhigh research and motor octane (low sensitivity) numbers, contains noolefins or aromatics and little or no sulfur, demonstrates excellentstability and is clean burning. One measure of the selectivity of analkylation catalyst is the C₉ + yield. This fraction generally resultsfrom oligomerization of the feed olefins resulting in a loss of alkylateyield, reduced alkylate quality and the possible formation of an acidicsludge fraction.

The product produced by the process of this invention may be of highquality based on both research and motor octane numbers and as such maybe particularly well suited for blending into the gasoline pool.

The process of the present invention may take place in the presence of acatalyst. Examples of such catalysts include MCM-22 and MCM-36.

MCM-36 and methods for its preparation are described in U.S. Pat. No.5,250,277, the entire disclosure of which is expressly incorporatedherein by reference.

MCM-36 may be prepared from an intermediate material which iscrystallized in the presence of a hexamethyleneimine directing agent andwhich, if calcined, without being swollen would be transformed into amaterial having an X-ray diffraction pattern as shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Interplanar        Relative Intensity,                                        d-Spacing (A)      I/I.sub.o × 100                                      ______________________________________                                        30.0 ± 2.2      w-m                                                        22.1 ± 1.3      w                                                          12.36 ± 0.2     m-vs                                                       11.03 ± 0.2     m-s                                                        8.83 ± 0.14     m-vs                                                       6.86 ± 0.14     w-m                                                        6.18 ± 0.12     m-vs                                                       6.00 ± 0.10     w-m                                                        5.54 ± 0.10     w-m                                                        4.92 ± 0.09     w                                                          4.64 ± 0.08     w                                                          4.41 ± 0.08     w-m                                                        4.25 ± 0.08     w                                                          4.10 ± 0.07     w-s                                                        4.06 ± 0.07     w-s                                                        3.91 ± 0.07     m-vs                                                       3.75 ± 0.06     w-m                                                        3.56 ± 0.06     w-m                                                        3.42 ± 0.06     vs                                                         3.30 ± 0.05     w-m                                                        3.20 ± 0.05     w-m                                                        3.14 ± 0.05     w-m                                                        3.07 ± 0.05     w                                                          2.99 ± 0.05     w                                                          2.82 ± 0.05     w                                                          2.78 ± 0.05     w                                                          2.68 ± 0.05     w                                                          2.59 ± 0.05     w                                                          ______________________________________                                    

The values in this Table and like tables presented hereinafter weredetermined by standard techniques. The radiation was the K-alpha doubletof copper and a diffractometer equipped with a scintillation counter andan associated computer was used. The peak heights, I, and the positionsas a function of 2 theta, where theta is the Bragg angle, weredetermined using algorithms on the computer associated with thediffractometer. From these, the relative intensities, 100 I/I_(o), whereI_(o) is the intensity of the strongest line or peak, and d (obs.) theinterplanar spacing in Angstrom Units (A), corresponding to the recordedlines, were determined. In Tables 1-8, the relative intensities aregiven in terms of the symbols w=weak, m=medium, s=strong and vs=verystrong. In terms of intensities, these may be generally designated asfollows:

w=0-20

m=20-40

s=40-60

vs=60-100

The material having the X-ray diffraction pattern of Table 1 is known asMCM-22 and is described in U.S. Pat. No. 4,954,325, the entiredisclosure of which is incorporated herein by reference. This materialcan be prepared from a reaction mixture containing sources of alkali oralkaline earth metal (M), e.g., sodium or potassium, cation, an oxide oftrivalent element X, e.g., aluminum, an oxide of tetravalent element Y,e.g., silicon, an organic (R) directing agent, hereinafter moreparticularly described, and water, said reaction mixture having acomposition, in terms of mole ratios of oxides, within the followingranges:

    ______________________________________                                        Reactants       Useful   Preferred                                            ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                      10-80   10-60                                                H.sub.2 O/YO.sub.2                                                                              5-100  10-50                                                OH.sup.- /YO.sub.2                                                                            0.01-1.0 0.1-0.5                                              M/YO.sub.2      0.01-2.0 0.1-1.0                                              R/YO.sub.2      0.05-1.0 0.1-0.5                                              ______________________________________                                    

In the synthesis method for preparing the material having the X-raydiffraction pattern of Table 1, the source of YO₂ must be comprisedpredominately of solid YO₂, for example at least about 30 wt. % solidYO₂ in order to obtain the desired crystal product. Where YO₂ is silica,the use of a silica source containing at least about 30 wt. % solidsilica, e.g., Ultrasil (a precipitated, spray dried silica containingabout 90 wt. % silica) or HiSil (a precipitated hydrated SiO₂ containingabout 87 wt. % silica, about 6 wt. % free H₂ O and about 4.5 wt. % boundH₂ O of hydration and having a particle size of about 0.02 micron)favors crystal formation from the above mixture and is a distinctimprovement over the synthesis method taught in U.S. Pat. No. 4,439,409.If another source of oxide of silicon e.g., Q-Brand (a sodium silicatecomprised of about 28.8 wt. % SiO₂, 8.9 wt. % Na₂ O and 62.3 wt. % H₂ O)is used, crystallization yields little or none of the crystallinematerial having the X-ray diffraction pattern of Table 1. Impurityphases of other crystal structures, e.g., ZSM-12, are prepared in thelatter circumstance. Preferably, therefore, the YO₂, e.g., silica,source contains at least about 30 wt. % solid YO₂, e.g., silica, andmore preferably at least about 40 wt. % solid YO₂, e.g., silica.

Crystallization of the crystalline material having the X-ray diffractionpattern of Table 1 can be carried out at either static or stirredconditions in a suitable reactor vessel, such as for example,polypropylene jars or teflon lined or stainless steel autoclaves. Thetotal useful range of temperatures for crystallization is from about 80°C. to about 225° C. for a time sufficient for crystallization to occurat the temperature used, e.g., from about 24 hours to about 60 days.Thereafter, the crystals are separated from the liquid and recovered.

The organic directing agent for use in synthesizing the presentcrystalline material from the above reaction mixture may behexamethyleneimine which has the following structural formula: ##STR1##Other organic directing agents which may be used include1,4-diazacycloheptane, azacyclooctane, aminocyclohexane,aminocycloheptane, aminocyclopentane,N,N,N-trimethyl-1-adamantanammonium ions, andN,N,N-trimethyl-2-adamantanammonium ions. In general, the organicdirecting agent may be selected from the group consisting ofheterocyclic imines, cycloalkyl amines and adamantane quaternaryammonium ions.

It should be realized that the reaction mixture components can besupplied by more than one source. The reaction mixture can be preparedeither batchwise or continuously. Crystal size and crystallization timeof the crystalline material will vary with the nature of the reactionmixture employed and the crystallization conditions.

Synthesis of crystals may be facilitated by the presence of at least0.01 percent, e.g., 0.10 percent or 1 percent, seed crystals (based ontotal weight) of crystalline product.

The crystalline material having the X-ray diffraction pattern of Table 1passes through an intermediate stage. The material at this intermediatestage has a different X-ray diffraction pattern than that set forth inTable 1. It has further been discovered that this intermediate materialis swellable with the use of suitable swelling agents such ascetyltrimethylammonium compounds, e.g., cetyltrimethylammoniumhydroxide. However, when this swollen intermediate material is calcined,even under mild conditions, whereby the swelling agent is removed, thematerial can no longer be swollen with such swelling agent. By way ofcontrast it is noted that various layered silicates such as magadiiteand kenyaite may be swellable with cetyltrimethylammonium compounds bothprior to and after mild calcination.

The present swollen products may have relatively high interplanardistance (d-spacing), e.g., greater than about 6 Angstrom, e.g., greaterthan about 10 Angstrom and even exceeding 30 Angstrom. These swollenmaterials may be converted into pillared materials. These pillaredmaterials, particularly silica pillared materials, may be capable ofbeing exposed to severe conditions such as those encountered incalcining, e.g., at temperatures of about 450° C. for about two or morehours, e.g., four hours, in nitrogen or air, without significantdecrease, e.g., less than about 10%, in interlayer distance.

The material having the X-ray diffraction pattern of Table 1, whenintercepted in the swellable, intermediate state, prior to finalcalcination, may have the X-ray diffraction pattern shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        d(A)                   I/I.sub.o                                              ______________________________________                                        13.53 ± 0.2         m-vs                                                   12.38 ± 0.2         m-vs                                                   11.13 ± 0.2         w-s                                                    9.15 ± 0.15         w-s                                                    6.89 ± 0.15         w-m                                                    4.47 ± 0.10         w-m                                                    3.95 ± 0.08         w-vs                                                   3.56 ± 0.06         w-m                                                    3.43 ± 0.06         m-vs                                                   3.36 ± 0.05         w-s                                                    ______________________________________                                    

An X-ray diffraction pattern trace for an example of such anas-synthesized, swellable material is shown in FIG. 1. A particularexample of such an as-synthesized, swellable material is the material ofExample 1 of the aforementioned U.S. Pat. No. 4,954,325. This materialof Example 1 of U.S. Pat. No. 4,954,325 has the X-ray diffractionpattern given in the following Table 3.

                  TABLE 3                                                         ______________________________________                                        2 Theta        d(A)    I/I.sub.o × 100                                  ______________________________________                                        3.1            28.5    14                                                     3.9            22.7    <1                                                     6.53           13.53   36                                                     7.14           12.38   100                                                    7.94           11.13   34                                                     9.67           9.15    20                                                     12.85          6.89    6                                                      13.26          6.68    4                                                      14.36          6.17    2                                                      14.70          6.03    5                                                      15.85          5.59    4                                                      19.00          4.67    2                                                      19.85          4.47    22                                                     21.56          4.12    10                                                     21.94          4.05    19                                                     22.53          3.95    21                                                     23.59          3.77    13                                                     24.98          3.56    20                                                     25.98          3.43    55                                                     26.56          3.36    23                                                     29.15          3.06    4                                                      31.58          2.833   3                                                      32.34          2.768   2                                                      33.48          2.676   5                                                      34.87          2.573   1                                                      36.34          2.472   2                                                      37.18          2.418   1                                                      37.82          2.379   5                                                      ______________________________________                                    

Taking into account certain modifications, this swellable material maybe swollen and pillared by methods generally discussed in theaforementioned U.S. Pat. No. 4,859,648, the entire disclosure of whichis expressly incorporated herein be reference. The present modificationsare discussed hereinafter and include the selection of proper swellingpH and swelling agent.

Upon being swollen with a suitable swelling agent, such as acetyltrimethylammonium compound, the swollen material may have the X-raydiffraction pattern shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        d(A)                   I/I.sub.o                                              ______________________________________                                        >32.2                  vs                                                     2.41 ± 0.25         w-s                                                    3.44 ± 0.07         w-s                                                    ______________________________________                                    

The X-ray diffraction pattern of this swollen material may haveadditional lines with a d(A) spacing less than the line at 12.41±0.25,but none of said additional lines have an intensity greater than theline at the d(A) spacing of 12.41±0.25 or at 3.44±0.07, whichever ismore intense. More particularly, the X-ray diffraction pattern of thisswollen material may have the lines shown in the following Table 5.

                  TABLE 5                                                         ______________________________________                                        d(A)                   I/I.sub.o                                              ______________________________________                                        >32.2                  vs                                                     12.41 ± 0.25        w-s                                                    11.04 ± 0.22        w                                                      9.28 ± 0.19         w                                                      6.92 ± 0.14         w                                                      4.48 ± 0.09         w-m                                                    3.96 ± 0.08         w-m                                                    3.57 ± 0.07         w-m                                                    3.44 ± 0.07         w-s                                                    3.35 ± 0.07         w                                                      ______________________________________                                    

Even further lines may be revealed upon better resolution of the X-raydiffraction pattern. For example, the X-ray diffraction pattern may haveadditional lines at the following d(A) spacings (intensities given inparentheses): 16.7±4.0 (w-m); 6.11±0.24 (w); 4.05±0.08 (w); and3.80±0.08 (w).

In the region with d<9 A, the pattern for the swollen material isessentially like the one given in Table 2 for the unswollen material,but with the possibility of broadening of peaks.

An X-ray diffraction pattern trace for an example of such a swollenmaterial is shown in FIG. 2. The upper profile is a 10-foldmagnification of the lower profile in FIG. 2.

Upon being pillared with a suitable polymeric oxide, such as polymericsilica, the swollen material having the X-ray diffraction pattern shownin Table 4 may be converted into a material having the X-ray diffractionpattern shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        d(A)                   I/I.sub.o                                              ______________________________________                                        >32.2                  vs                                                     12.38 ± 0.25        w-m                                                     3.42 ± 0.07        w-m                                                    ______________________________________                                    

The X-ray diffraction pattern of this pillared material may haveadditional lines with a d(A) spacing less than the line at 12.38±0.25,but none of said additional lines have an intensity greater than theline at the d(A) spacing of 12.38±0.25 or 3.42±0.07, whichever is moreintense. More particularly, the X-ray diffraction pattern of thispillared material may have the lines shown in the following Table 7.

                  TABLE 7                                                         ______________________________________                                        d(A)                   I/I.sub.o                                              ______________________________________                                        >32.2                  vs                                                     12.38 ± 0.25        w-m                                                    10.94 ± 0.22        w-m                                                    9.01 ± 0.18         w                                                      6.88 ± 0.14         w                                                      6.16 ± 0.12         w-m                                                    3.93 ± 0.08         w-m                                                    3.55 ± 0.07         w                                                      3.42 ± 0.07         w-m                                                    3.33 ± 0.07         w-m                                                    ______________________________________                                    

Even further lines may be revealed upon better resolution of the X-raydiffraction pattern. For example, the X-ray diffraction pattern may haveadditional lines at the following d(A) spacings (intensities given inparentheses): 5.59±0.11 (w); 4.42±0.09 (w); 4.11±0.08 (w); 4.04±0.08(w); and 3.76±0.08 (w).

An X-ray diffraction pattern trace for an example of such a pillaredmaterial is given in FIG. 3. The upper profile is a 10-foldmagnification of the lower profile in FIG. 3.

If the material swollen with a suitable swelling agent is calcinedwithout prior pillaring another material is produced. For example, ifthe material which is swollen but not pillared is calcined in air for 6hours at 540° C., a very strong line at a d(A) spacing of greater than32.2 will no longer be observed. By way of contrast, when the swollen,pillared material is calcined in air for 6 hours at 540° C., a verystrong line at a d(A) spacing of greater than 32.2 will still beobserved, although the precise position of the line may shift.

An example of a swollen, non-pillared material, which has been calcined,has the pattern as shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        2 Theta    d(A)           I/I.sub.o × 100                               ______________________________________                                        3.8        23.3           12                                                  7.02       12.59          100                                                 8.02       11.02          20                                                  9.66       9.16           14                                                  12.77      6.93           7                                                   14.34      6.18           45                                                  15.75      5.63           8                                                   18.19      4.88           3                                                   18.94      4.69           3                                                   19.92      4.46           13     broad                                        21.52      4.13           13     shoulder                                     21.94      4.05           18                                                  22.55      3.94           32                                                  23.58      3.77           16                                                  24.99      3.56           20                                                  25.94      3.43           61                                                  26.73      3.33           19                                                  31.60      2.831          3                                                   33.41      2.682          4                                                   34.62      2.591          3      broad                                        36.36      2.471          1                                                   37.81      2.379          4                                                   ______________________________________                                    

The X-ray powder pattern shown in Table 8 is similar to that shown inTable 1 except that most of the peaks in Table 8 are much broader thanthose in Table 1.

An X-ray diffraction pattern trace for an example of the calcinedmaterial corresponding to Table 8 is given in FIG. 4.

As mentioned previously, the calcined material corresponding to theX-ray diffraction pattern of Table 1 is designated MCM-22. For thepurposes of the present disclosure, the pillared material correspondingto the X-ray diffraction pattern of Table 6 is designated herein asMCM-36. The swollen material corresponding to the X-ray diffractionpattern of Table 4 is designated herein as the swollen MCM-22 precursor.The as-synthesized material corresponding to the X-ray diffractionpattern of Table 2 is referred to herein, simply, as the MCM-22precursor.

The layers of the swollen material of this disclosure may have acomposition involving the molar relationship:

    X.sub.2 O.sub.3 :(n)YO.sub.2,

wherein X is a trivalent element, such as aluminum, boron, iron and/orgallium, preferably aluminum, Y is a tetravalent element such as siliconand/or germanium, preferably silicon, and n is at least about 5, usuallyfrom about 10 to about 150, more usually from about 10 to about 60, andeven more usually from about 10 to about 40.

To the extent that the layers of the swollen MCM-22 precursor and MCM-36have negative charges, these negative charges are balanced with cations.For example, expressed in terms of moles of oxides, the layers of theswollen MCM-22 precursor and MCM-36 may have a ratio of 0.5 to 1.5 R₂O:X₂ O₃, where R is a monovalent cation or 1/m of a cation of valency m.

MCM-36 adsorbs significant amounts of commonly used test adsorbatematerials, i.e., cyclohexane, n-hexane and water. Adsorption capacitiesfor this pillared material, especially the silica pillared material, mayrange at room temperature as follows:

    ______________________________________                                        Adsorbate    Capacity, Wt. Percent                                            ______________________________________                                        n-hexane     17-40                                                            cyclohexane  17-40                                                            water        10-40                                                            ______________________________________                                    

wherein cyclohexane and n-hexane sorption are measured at 20 Torr andwater sorption is measured at 12 Torr.

The swellable material, used to form the swollen material of the presentdisclosure, may be initially treated with a swelling agent. Suchswelling agents are materials which cause the swellable layers toseparate by becoming incorporated into the interspathic region of theselayers. The swelling agents are removable by calcination, preferably inan oxidizing atmosphere, whereby the swelling agent becomes decomposedand/or oxidized.

Suitable swelling agents may comprise a source of organic cation, suchas quaternary organoammonium or organophosphonium cations, in order toeffect an exchange of interspathic cations. Organoammonium cations, suchas n-octylammonium, showed smaller swelling efficiency than, forexample, cetyltrimethylammonium. A pH range of 11 to 14, preferably 12.5to 13.5 is generally employed during treatment with the swelling agent.

The as-synthesized material is preferably not dried prior to beingswollen. This as-synthesized material may be in the form of a wet cakehaving a solids content of less than 30% by weight, e.g., 25 wt % orless.

The foregoing swelling treatment results in the formation of a layeredoxide of enhanced interlayer separation depending upon the size of theorganic cation introduced. In one embodiment, a series of organic cationexchanges can be carried out. For example, an organic cation may beexchanged with an organic cation of greater size, thus increasing theinterlayer separation in a step-wise fashion. When contact of thelayered oxide with the swelling agent is conducted in aqueous medium,water is trapped between the layers of the swollen species.

The organic-swollen species may be treated with a compound capable ofconversion, e.g., by hydrolysis and/or calcination, to pillars of anoxide, preferably to a polymeric oxide. Where the treatment involveshydrolysis, this treatment may be carried out using the water alreadypresent in organic-swollen material. In this case, the extent ofhydrolysis may be modified by varying the extent to which theorganic-swollen species is dried prior to addition of the polymericoxide precursor.

It is preferred that the organic cation deposited between the layers becapable of being removed from the pillared material without substantialdisturbance or removal of the interspathic polymeric oxide. For example,organic cations such as cetyltrimethylammonium may be removed byexposure to elevated temperatures, e.g., calcination, in nitrogen orair, or by chemical oxidation preferably after the interspathicpolymeric oxide precursor has been converted to the polymeric oxidepillars in order to form the pillared layered product.

These pillared layered products, especially when calcined, exhibit highsurface area, e.g., greater than 500 m² /g, and thermal and hydrothermalstability making them highly useful as catalysts or catalytic supports,for hydrocarbon conversion processes, for example, alkylation.

Insertion of the organic cation between the adjoining layers serves tophysically separate the layers in such a way as to make the layeredmaterial receptive to the interlayer addition of a polymeric oxideprecursor. In particular, cetyltrimethylammonium cations have been founduseful. These cations are readily incorporated within the interlayerspaces of the layered oxide serving to prop open the layers in such away as to allow incorporation of the polymeric oxide precursor. Theextent of the interlayer spacing can be controlled by the size of theorganoammonium ion employed.

Interspathic oxide pillars, which may be formed between the layers ofthe propped or swollen oxide material, may include an oxide, preferablya polymeric oxide, of zirconium or titanium or more preferably of anelement selected from Group IVB of the Periodic Table (FischerScientific Company Cat. No. 5-702-10, 1978), other than carbon, i.e.,silicon, germanium, tin and lead. Other suitable oxides include those ofGroup VA, e.g., V, Nb, and Ta, those of Group IIA, e.g., Mg or those ofGroup IIIB, e.g., B. Most preferably, the pillars include polymericsilica. In addition, the oxide pillars may include an element whichprovides catalytically active acid sites in the pillars, preferablyaluminum.

The oxide pillars are formed from a precursor material which may beintroduced between the layers of the organic "propped" species as anionic or electrically neutral compound of the desired elements, e.g.,those of Group IVB. The precursor material may be an organometalliccompound which is a liquid under ambient conditions. In particular,hydrolyzable compounds, e.g., alkoxides, of the desired elements of thepillars may be utilized as the precursors. Suitable polymeric silicaprecursor materials include tetraalkylsilicates, e.g.,tetrapropylorthosilicate, tetramethylorthosilicate and, most preferably,tetraethylorthosilicate. Suitable polymeric silica precursor materialsalso include quaternary ammonium silicates, e.g., tetramethylammoniumsilicate (i.e., TMA silicate). Where the pillars also include polymericalumina, a hydrolyzable aluminum compound can be contacted with theorganic "propped" species before, after or simultaneously with thecontacting of the propped layered oxide with the silicon compound.Preferably, the hydrolyzable aluminum compound employed is an aluminumalkoxide, e.g., aluminum isopropoxide. If the pillars are to includetitania, a hydrolyzable titanium compound such as titanium alkoxide,e.g., titanium isopropoxide, may be used.

After calcination to remove the organic propping agent, the finalpillared product may contain residual exchangeable cations. Suchresidual cations in the layered material can be ion exchanged by knownmethods with other cationic species to provide or alter the catalyticactivity of the pillared product. Suitable replacement cations includecesium, cerium, cobalt, nickel, copper, zinc, manganese, platinum,lanthanum, aluminum, ammonium, hydronium and mixtures thereof.

Particular procedures for intercalating layered materials with metaloxide pillars are described in U.S. Pat. Nos. 4,831,005; 4,831,006; and4,929,587. The entire disclosures of these patents are expresslyincorporated herein by reference. U.S. Pat. No. 4,831,005 describesplural treatments with the pillar precursor. U.S. Pat. No. 4,929,587describes the use of an inert atmosphere, such as nitrogen, to minimizethe formation of extralaminar polymeric oxide during the contact withthe pillar precursor. U.S. Pat. No. 4,831,006 describes the use ofelevated temperatures during the formation of the pillar precursor.

The resulting pillared products exhibit thermal stability attemperatures of 450° C. or even higher as well as substantial sorptioncapacities (as much as 17 to 40 wt % for C₆ hydrocarbon). The pillaredproducts may possess a basal spacing of at least about 32.2 A andsurface areas greater than 500 m² /g.

The layered material may be subjected to thermal treatment, e.g., todecompose organoammonium ions. This thermal treatment is generallyperformed by heating one of these forms at a temperature of at leastabout 370° C. for at least 1 minute and generally not longer than 20hours. While subatmospheric pressure can be employed for the thermaltreatment, atmospheric pressure is preferred simply for reasons ofconvenience.

Prior to its use as a catalyst, MCM-36 should be subjected to thermaltreatment to remove part or all of any organic constituent presenttherein.

MCM-36 can optionally be used in intimate combination with ahydrogenating component such as tungsten, vanadium, molybdenum, rhenium,nickel, cobalt, chromium, manganese, or a noble metal such as platinumor palladium where a hydrogenation-dehydrogenation function is to beperformed. MCM-36 can also optionally be used in intimate combinationwith a rare earth component such as lanthanum or cerium. Such componentcan be associated chemically and/or physically with the MCM-36 and/ormatrix with which the MCM-36 may be optionally composited. Thus, e.g.,the hydrogenating component can be introduced into the catalystcomposition by way of co-crystallization, exchanged into the compositionto the extent a Group IIIA element, e.g., aluminum, is in the structure,impregnated therein or intimately physically admixed therewith. Suchcomponent can be impregnated in, or on, the MCM-36 such as, for example,by, in the case of platinum, treating the MCM-36 with a solutioncontaining the platinum metal-containing ion. Thus, suitable platinumcompounds for this purpose include chloroplatinic acid, platinouschloride and various compounds containing the platinum amine complex.

The MCM-36, especially in its metal, hydrogen and ammonium forms, can bebeneficially converted to another form by thermal treatment. Thisthermal treatment is generally performed by heating one of these formsat a temperature of at least about 370° C. for at least 1 minute andgenerally not longer than 20 hours. While subatmospheric pressure can beemployed for the thermal treatment, atmospheric pressure is preferredsimply for reasons of convenience. The thermal treatment can beperformed at a temperature of up to about 925° C.

Prior to its use as a catalyst, the MCM-36 crystals may be at leastpartially dehydrated. This dehydration can be accomplished by heatingthe MCM-36 to a temperature in the range of from about 200° C. to about595° C. in an atmosphere such as air, nitrogen, etc., and atatmospheric, subatmospheric or superatmospheric pressures for a periodof from between about 30 minutes to about 48 hours. Dehydration can alsobe performed at room temperature merely by placing the MCM-36 in avacuum but a longer time will be required to achieve a suitable degreeof dehydration.

The MCM-36 can be shaped into a wide variety of particle sizes.Generally speaking, the particles can be provided in the form of apowder, a granule or a molded product such as an extrudate having aparticle size sufficient to pass through a 2 mesh (Tyler) screen and besubstantially retained on a 400 mesh (Tyler) screen. In cases where thecatalyst is molded, such as by extrusion, the crystals can be extrudedbefore drying or partially dried and then extruded.

It may be desired to incorporate the MCM-36 with another material, i.e.,a binder, which is resistant to the temperatures and other conditionsemployed in the isoparaffin alkylation process of this invention.Suitable binder materials include active and inactive materials andsynthetic or naturally occurring zeolites as well as inorganic materialssuch as clays, silica and/or metal oxides such as alumina. The lattercan be either naturally occurring or provided in the form of gelatinousprecipitates or gels including mixtures of silica and metal oxides. Useof a binder material in conjunction with MCM-36, i.e., combinedtherewith or present during its synthesis, which itself is catalyticallyactive may change the conversion and/or selectivity of the catalyst.Inactive materials suitably serve as diluents to control the amount ofconversion so that products can be obtained economically and in acontrolled fashion without having to employ other means for controllingthe rate of reaction. These materials can be incorporated into naturallyoccurring clays, e.g., bentonite and kaolin, to improve the crushstrength of the MCM-36 under commercial operating conditions. Good crushstrength is an advantageous attribute for commercial use since itprevents or delays breaking down of the catalyst into powder-likematerials.

Naturally occurring clays which can be composited with MCM-36 crystalsinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with MCM-36 also include inorganicoxides, notably alumina.

Apart from or in addition to the foregoing binder materials, the MCM-36crystals can be composited with an inorganic oxide matrix such assilica-alumina, silica-magnesia, silica-zirconia, silica-thoria,silica-beryllia, silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia,silica-magnesia-zirconia, etc. It may be advantageous to provide atleast a part of the foregoing matrix materials in colloidal form so asto facilitate extrusion of the bound catalyst component(s).

The relative proportions of finely divided MCM-36 and inorganic oxidematrix can vary widely with the MCM-36 content ranging from about 1 toabout 95 percent by weight and more usually, particularly when thecomposite is prepared in the form of beads, in the range of about 2 toabout 80 weight percent of the composite.

Other catalytic materials may be used in the present process in place ofMCM-36. These materials include zeolites, especially acid zeolites suchas MCM-22. These catalytic materials may be combined with a binderand/or a hydrogenation/dehydrogenation component in the same mannerdescribed hereinabove for MCM-36.

The operating temperature of the hydrogen transfer or the dual hydrogentransfer/alkylation process described herein can extend over a fairlybroad range, e.g., from about -25° to about 400° C., and is preferablywithin the range of from about 75° C. to about 200° C. The practicalupper operating temperature will often be dictated by the need to avoidan undue occurrence of undesirable side reactions.

The pressures employed in the present process can extend over aconsiderably wide range, e.g., from subatmospheric pressure to about5000 psig, and preferably from atmospheric pressure to about 2000 psig.

The amount of catalyst, such as MCM-36, used in the present hydrogentransfer or dual hydrogen transfer/alkylation process can be varied overrelatively wide limits. In general, the amount of catalyst as measuredby the weight hourly space velocity (WHSV) based on olefin can rangefrom about 0.01 to about 100 hr⁻¹ preferably from 0.05 to 5 hr⁻¹. Itwill, of course, be realized by those skilled in the art that the amountof catalyst selected for a particular reaction will be determined byseveral variables including the reactants involved as well as the natureof the catalyst and the operating conditions employed.

The paraffin feed may comprise one or more paraffins, especiallyisoparaffins. The paraffin or isoparaffin reactant used in the presentalkylation process may be one possessing up to about 20 carbon atoms andpreferably one having from about 4 to about 8 carbon atoms as, forexample, isobutane, 3-methylhexane, 2-methylbutane, 2,3-dimethylbutaneand 2,4-dimethylhexane.

The olefin feed may comprise one or more branched olefins. The olefinreactant employed herein generally contains from 5 to about 12 carbonatoms. Representative examples are branched forms of pentenes, hexenes,heptenes and octenes. Particular olefin feeds may comprise one or moreolefins having from 5 to 8, e.g. 6 to 8, carbon atoms.

Olefinic feedstocks suitable for use in the present invention includenumerous olefinic streams produced by petroleum refining operations, forexample, a cracking operation. In a particular cracking operation, acracked olefinic stream such as an olefinic gasoline boiling rangefraction is produced from a delayed coker process unit. Delayed cokingprocesses are taught in U.S. Pat. No. 3,917,564 to Meyers and U.S. Pat.No. 4,874,505 to Bartilucci et al., both of which patents areincorporated herein by reference.

Suitable olefinic feedstocks are also produced as byproducts incatalytic dewaxing processes. An example of such a process is describedin U.S. Pat. No. 4,922,048, which patent is incorporated herein byreference.

Suitable olefinic feedstocks may also be produced during oligomerizationprocesses, such as MOGD and MOGDL, which are described more fullyhereinafter.

Recent developments in zeolite catalysts and hydrocarbon conversionmethods and apparatuses have created interest in utilizing olefinicfeedstocks for producing heavier hydrocarbons, such as C₅ + gasoline,distillate or lubes. These developments form the basis of the Mobilolefins to gasoline/distillate (MOGD) method and apparatus, and theMobil olefins to gasoline/distillate/lubes (MOGDL) method and apparatus.

In MOGD and MOGDL, olefins are catalytically converted to heavierhydrocarbons by catalytic oligomerization using an acid crystallinezeolite, such as a zeolite catalyst having the structure of ZSM-5.Process conditions can be varied to favor the formation of eithergasoline, distillate or lube range products. U.S. Pat. Nos. 3,960,978and 4,021,502 to Plank et al. disclose the conversion of C₂ -C₅ olefinsalone or in combination with paraffinic components, into higherhydrocarbons over a crystalline zeolite catalyst. U.S. Pat. Nos.4,150,062; 4,211,640 and 4,227,992 to Garwood et al. have contributedimproved processing techniques to the MOGD system. U.S. Pat. No.4,456,781 to Marsh et al. has also disclosed improved processingtechniques for the MOGD system.

Olefinic feedstocks may be obtained from various sources, including fromfossil fuel processing streams such as gas separation units, from thecracking of C₂ -hydrocarbons, such as LPG (liquified petroleum gas) fromcoal by-products, from various synthetic fuel processing streams, and asby-products from fluid catalytic cracking (FCC) and thermal catalyticcracking (TCC) process units. U.S. Pat. No. 4,100,218 to Chen et al.teaches thermal cracking of ethane to ethylene, with subsequentconversion of ethylene to LPG and gasoline over a zeolite catalysthaving the structure of ZSM-5.

In general, the mole ratio of total paraffin or isoparaffin to totalolefin in the combined hydrocarbon feed can be from about 1:2 to about500:1 and is preferably in the range of from about 5:1 to about 50:1.The paraffin, isoparaffin and/or olefin reactants can be in either thevapor phase or the liquid phase and can be neat, i.e., free fromintentional admixture of dilution with other material, or the reactantscan be brought into contact with the catalyst composition with the aidof carrier gases or diluents such as, for example, hydrogen or nitrogen.The reactants also may optionally be introduced to the reaction zonetogether with one or more other reactive materials which serve toenhance the overall conversion operation.

The process of the present invention can be carried out as a batch-type,semi-continuous or continuous operation utilizing a fixed or moving bedof the catalyst component. A preferred embodiment entails use of acatalyst zone wherein the hydrocarbon charge is passed concurrently orcountercurrently through a moving bed of particle-form catalyst. Thelatter, after use, is conducted to a regeneration zone where coke isremoved, e.g., by burning in an oxygen-containing atmosphere (such asair) at elevated temperature or by extracting with a solvent, afterwhich the regenerated catalyst is recycled to the conversion zone forfurther contact with the organic reactants.

In order to more fully illustrate the process of this invention and themanner of practicing same, the following examples are presented. Inexamples illustrative of the synthesis of MCM-36, whenever sorption dataare set forth for comparison of sorptive capacities for water,cyclohexane and/or n-hexane, they were Equilibrium Adsorption valuesdetermined as follows:

A weighed sample of the calcined adsorbent was contacted with thedesired pure adsorbate vapor in an adsorption chamber, evacuated to lessthan 1 mm Hg and contacted with 12 Torr of water vapor or 40 Torr ofn-hexane or 40 Torr of cyclohexane vapor, pressures less than thevapor-liquid equilibrium pressure of the respective adsorbate at 90° C.The pressure was kept constant (within about ±0.5 mm Hg) by addition ofadsorbate vapor controlled by a manostat during the adsorption period,which did not exceed about 8 hours. As adsorbate was adsorbed by theabsorbent, the decrease in pressure caused the manostat to open a valvewhich admitted more adsorbate vapor to the chamber to restore the abovecontrol pressures. Sorption was complete when the pressure change wasnot sufficient to activate the manostat. The increase in weight wascalculated as the adsorption capacity of the sample in g/100 g ofcalcined adsorbant.

EXAMPLE 1

A combination of 504 g of water, 11.4 g of 50% sodium hydroxide, 11.4 gof sodium aluminate (43.5% Al₂ O₃, 30% Na₂ O), 64.9 g of silica(Ultrasil) and 34.2 g of hexamethyleneimine was reacted in an autoclaveat 143° C. for 48 hours with stirring. The product was filtered andwashed thoroughly with water.

500 g of the wet cake material (24% solids) described above was mixedwith 3 1 of 29% CTMA-OH (cetyltrimethylammonium hydroxide-pH=13.5,obtained by anion exchange of 29% CTMA-Cl with 0.9 l of IRA-400(OH) fromALPHA) and stirred for 48 hours at room temperature. The swollen productwas isolated by filtration, washed twice with 500 ml of water and airdried overnight. The X-ray diffraction pattern for this swollen materialis given in the following Table 9.

                  TABLE 8                                                         ______________________________________                                        2 Theta   d(A)         I/I.sub.o × 100                                  ______________________________________                                        1.7       52.0         100                                                    5.18      17.06        7.3                                                    6.81      12.98        2.3                                                    7.10      12.45        5.7                                                    8.79      10.06        2.7    very broad                                      12.73     6.95         0.6                                                    13.82     6.41         0.4                                                    14.55     6.09         0.3                                                    15.59     5.68         0.7                                                    18.39     4.82         1.3    broad shoulder                                  19.06     4.66         2.6    shoulder                                        19.77     4.49         4.8                                                    21.01     4.23         3.4    broad                                           22.28     3.99         5.0                                                    23.35     3.81         2.3    broad shoulder                                  24.91     3.57         3.0                                                    25.90     3.44         8.0                                                    26.50     3.36         4.4                                                    ______________________________________                                    

235 g of this swollen material was ground and combined with 1.4 liter ofTEOS (tetraethylorthosilicate). The TEOS treated material was heatedunder a stream of nitrogen. After filtration and drying the product washydrolyzed in water. The pillared product contained 65% solids based oncalcination at 540° C.

The X-ray diffraction pattern for this pillared, calcined material isgiven in the following Table 10.

                  TABLE 10                                                        ______________________________________                                        2 Theta    d(A)           I/I.sub.o × 100                               ______________________________________                                        1.7        52.0           100                                                 7.13       12.40          23.3                                                8.08       10.94          7.3    broad                                        12.84      6.89           1.5                                                 14.38      6.16           8.4                                                 15.83      5.60           0.9                                                 19.88      4.47           2.3    broad                                        21.61      4.11           2.2                                                 22.07      4.03           3.3    broad                                        22.67      3.92           4.3    broad                                        23.67      3.76           2.7                                                 25.06      3.55           4.0                                                 26.06      3.42           12.8                                                26.75      3.33           4.1                                                 ______________________________________                                    

EXAMPLE 2

An alumina-bound MCM-36 catalyst was prepared by mulling and thenextruding (1/16" extrudate) a 65/35 (wt./wt.) mixture of MCM-36(prepared as described in above Example 1) and Versal 250 alumina. Theextrudate product was then dried at 250° F. overnight. After drying, theMCM-36 extrudate was calcined by the following method: 3 hr in nitrogenat 450° C. followed by slow bleeding of air and full air calcination at540° C. for 6 hours. Following calcination, the extrudate was exchangedwith 1N NH₄ NO₃, washed with deionized water, recalcined at 540° C. for3 hours and finally crushed and sized to 30/60 mesh for catalyticevaluation.

EXAMPLE 3

A sufficient amount of the extruded catalyst of Example 2 to provide 5.0g of MCM-36 was crushed and added to a 300 cc autoclave. Following asuccessful pressure test, 90 g of isobutane and 13 g of2,3-dimethyl-2-butene were charged to the reactor and the stirring rateincreased to 500 RPM. The pressure of the autoclave was increased to 150psig by adding nitrogen, and the temperature increased to 300° F. at arate of 5° F./min. Reactor pressure reached 700 psig after the maximumtemperature was reached. A sample of the hydrocarbon was taken 24 hoursafter the commencement of heating. Analysis of the reaction products wasperformed using a gas chromatograph equipped with a silica capillarycolumn. Results are given in Table 11. In Table 11, HC stands forhydrocarbon, IC₄ stands for isobutane, C₆ ⁼ stands for2,3-dimethyl-2-butene, TMP stands for trimethylpentane and DMH standsfor dimethylhexane.

                  TABLE 11                                                        ______________________________________                                        Production of C.sub.8 Isoparaffins During                                     Isobutane/C.sub.6 .sup.= Reactions                                            ______________________________________                                        Temp., °F.   300                                                       Pressure, psig      700                                                       HC/MCM-36, w/w      20                                                        Initial IC.sub.4 /C.sub.6.sup.=, mole ratio                                                       10                                                        Hours on Stream     24                                                        Olefin Conv., Wt %  97                                                        C.sub.5.sup.+  HC Dist., Wt %                                                 C.sub.5             8                                                         C.sub.6             23                                                        C.sub.7             8                                                         C.sub.8             24                                                        C.sub.9 +           38                                                        Normalized C.sub.8 Dist., Wt %                                                2,2,4 TMP           50                                                        2,3,4 TMP           12                                                        2,3,3 TMP           13                                                        2,5 DMH             9                                                         2,4 DMH             7                                                         2,3 DMH             6                                                         3,4 DMH             0                                                         Other C.sub.8 's    3                                                         TMP/DMH             3.4                                                       ______________________________________                                    

EXAMPLE 4

The procedure of Example 3 was repeated with a catalyst comprisingMCM-22, instead of MCM-36, as the active catalytic component. Theresults are given in Table 12.

                  TABLE 12                                                        ______________________________________                                        Production of C.sub.8 Isoparaffins During                                     Isobutane/C.sub.6 .sup.= Reactions                                            ______________________________________                                        Temp., °F.   300                                                       Pressure, psig      700                                                       HC/MCM-22, w/w      20                                                        Initial IC.sub.4 /C.sub.6.sup.=, mole ratio                                                       10                                                        Hours on Stream     24                                                        Olefin Conv., Wt %  97                                                        C.sub.5.sup.+  HC Dist., Wt %                                                 C.sub.5             4                                                         C.sub.6             29                                                        C.sub.7             5                                                         C.sub.8             14                                                        C.sub.9             47                                                        Normalized C.sub.8 Dist., Wt %                                                2,2,4 TMP           36                                                        2,3,4 TMP           6                                                         2,3,3 TMP           9                                                         2,5 DMH             9                                                         2,4 DMH             8                                                         2,3 DMH             11                                                        3,4 DMH             6                                                         Other C.sub.8 's    15                                                        TMP/DMH             1.5                                                       ______________________________________                                    

What is claimed is:
 1. A dual catalytic process for converting anisoparaffin feed and a branched C₅ + olefin feed, said processcomprising contacting both said isoparaffin feed and said olefin feedwith a catalyst comprising a zeolite under hydrogen transfer andalkylation reaction conditions, wherein the reaction conditions aresufficient to cause the following two results:(a) the transfer ofhydrogen from said isoparaffin feed to said olefin feed, wherebyisoparaffin feed is converted into olefin product and olefin feed isconverted into a first branched paraffin product, said olefin productbeing different from said olefin feed; and (b) said olefin product fromstep (a) alkylates with unreacted isoparaffin in said isoparaffin feedto produce a second branched paraffin product having the number ofcarbon atoms equal to the sum of the carbon atoms in the olefin andisoparaffin which are reacted together in this step (b).
 2. A processaccording to claim 1, wherein said isoparaffin feed comprises a singleisoparaffin compound.
 3. A process according to claim 1, wherein saidisoparaffin feed comprises more than one isoparaffin compound.
 4. Aprocess according to claim 1, wherein said olefin feed comprises asingle olefin compound.
 5. A process according to claim 1, wherein saidolefin feed comprises more than one olefin compound.
 6. A processaccording to claim 1, wherein said olefin feed comprises one or moreolefins having from 6 to 8 carbon atoms.
 7. A process according to claim1, wherein the mole ratio of total isoparaffin to total olefin in thefeed is from about 1:2 to about 100:1.
 8. A process according to claim1, wherein the reaction temperature is from about -25° C. to about 400°C., the pressure is from below atmospheric to about 5000 psig and theweight hourly space velocity based on olefin in the feed is from about0.01 to 100 hr⁻¹.
 9. A process according to claim 1, wherein theisoparaffin is isobutane and the olefin is 2,3-dimethyl-2-butene.
 10. Aprocess according to claim 1, wherein said zeolite is MCM-22.
 11. Aprocess for preparing branched paraffins, said process comprising thesteps of:(a) cracking hydrocarbons to produce a product comprising C₅ +branched olefins; (b) contacting the C₅ + branched olefins of step (a)with an isoparaffin feed and a catalyst comprising a zeolite underhydrogen transfer conditions, whereby isoparaffin feed is converted intoan olefin product and said C₅ + branched olefins are converted into afirst branched paraffin product; and (c) contacting said olefin productfrom step (b) with said catalyst and unreacted isoparaffin in saidisoparaffin feed under alkylation conditions to produce a secondbranched olefin product having the number of carbon atoms equal to thesum of the carbon atoms in the olefin and isoparaffin which are reactedtogether in step (c), wherein steps (b) and (c) take placesimultaneously in the same reactor.
 12. A process according to claim 11,wherein said isoparaffin is isobutane.
 13. A process according to claim11, wherein said zeolite is MCM-22.
 14. A process for preparing branchedparaffins, said process comprising the steps of:(a) oligomerizingolefins to produce a product comprising C₅ + branched olefins; (b)contacting the C₅ + branched olefins of step (a) with an isoparaffinfeed and a catalyst comprising a zeolite under hydrogen transferconditions, whereby isoparaffin feed is converted into an olefin productand said C₅ + branched olefins are converted into a first branchedparaffin product; and (c) contacting said olefin product from step (b)with said catalyst and unreacted isoparaffin in said isoparaffin feedunder alkylation conditions to produce a second branched olefin producthaving the number of carbon atoms equal to the sum of the carbon atomsin the olefin and isoparaffin which are reacted together in step (c),wherein steps (b) and (c) take place simultaneously in the same reactor.15. A process according to claim 14, wherein said isoparaffin isisobutane.
 16. A process according to claim 14, wherein said zeolite isMCM-22.